Organo-tin sulfonamides



Patented Apr. 7, i953 ORGANO-TIN SULFONAMIDES Gerry 'P. Mack, Jackson Heights, and Emery Parker, New York, N. Y., assignors to Advance Solventst Chemical Corporation, New York,

- NoDrawing. Original application August 9, 1949,

Serial No. 109,408. Divided and this application August 1, 1950, Serial 'No. 177,126

The invention is a division of our application, Serial No. 109,408 and relates to new organo-tin compounds.

The new compounds are organo-tin sulfonamides of the general formula wherein R represents an alkyl radical having 1 to 12 carbon atoms or an aryl-r-adicaLR' is hydrogen, alkyl or aryl, and R'flis alkyl, aryLor aralkyl; m is an integer from 2 to 3and-n is 2 for m=2and,1form=3.

[Ihe dialkyl and trialkyl tin sulfonamides are, depending on the sulfonamide and the dialkyl tin compoundused, odorless and colorless solids or viscous liquids of very low vapor pressure and are stable againstmoisture and air. They are soluble not only in hydrocarbons, esters and Siniilar conventionalsolvents but also in a number of high boiling esters used as plasticizers, such as dibutyl ,.phthalate, di ,2-ethy1 hexyl phthalate, butoxyethyl adipate, and many others; therefore they can be readily incorporated in vinyl halide resins with which they are fully compatible, and towhich they impart improved stability-against discoloration by prolonged exposure to heat and light.

. fI'he organo-tin sulfonamides of the inventior may be .prepared by causing .an alkali 'or an alkaline earth metal derivative of a sulfonamide to react with man organo-like dihalide or an or anortin monohalide. To carry out this reaction, the sulfonamide derivative is dispersed in an organic liquid, egg. .in an aromatic hydrocarbon which is asolvent for the dialkyl tin dihalide and "the formed organotin compound but does not take part in the reaction.

After completion of the reaction, the precipitatedalkali or alkaline earth metal halide is filteredoff and the formed organo-tin sulfonamide is recovered from the .solvent. The presence of water in this reactionis undesirable, as it will remove the halogen from the organotin halide and form an organo-tin oxide, which does not react.

Alkali metal derivatives of sulfonamides may be prepared by reacting the sulfonamide with metallic sodium or potassium, or with an alkoxide of a low molecular weight alcohol, such as methanol or ethanol, and by subsequently removing the alcohol though in some cases such removal is not necessary, Another method of preparation consists in subjecting the mixture of an alkali hydroxide and sulfonamide to azeotropic distillaion.

2 Claims. (Cl. 260-429) Aliphatic or aromatic 'sulfonamides may .Ihe used such as methyl, ethyl, butyl, hexyl, dodecyl, benzene, p. toluol, alpha andbeta naphthalene sulfonamide. 7

Also, alkylated aromatic sulfonamides -may-be used where one or more alkyl groups are attached to the aromatic nucleus, or aliphaticsulfon amides where one hydrogen of the amino group is replaced by an alkyl or 'aryl residue. Such sulfonamides result from thereaction between an aliphatic or aromatic "sulfochloride and a primary amine. Examples are: N-ethyl methane sulfonamide, N-butyl hexane sulfonamide, N

butyl benzene sulfonamide. TN-ethyl p. toluolsulfonamide, N-benzy'l butyl benzene suifon amide, N-isopropyl dodecyl benzene sul'fonamide, and others. 'Dialkyl tin dihalides suitable for the reaction with the alkali or alkaline earth metal sulionamides are for instance dimethyl, diethyl, dipropyl, dibutyl, diamyl, dioctyl, dilauryl tin dichloride "or the corresponding 'dibromides. f

The following examples will illustrate the preparation of the new compounds.

Eauample 1 68.4 g. of para-toluolsulfonamide, 1 6.4 g. of

caustic soda dissolved in 16 cc. of water and 3-00 cc. of xylol were refluxed until the theoretical amount of water was separated; the batch was then cooled under rapid stirring to disperse the sodium derivative of the para-toluolsulfonamide, which is insoluble in xylol. 60.8 g. of

dibutyl tin dichloride dissolved in 60. cc. of :Xylol were then slowly added at 0 to 5 C. and the To. facilitate the removal of-the sodium chloride formed, the

batch was heated to C. and filtered by suction. A clear yellowish solution was obtained from which the xylol was removed by vacuum distillation. The product. so obtained contained 19.34% of tin and consisted predominantly of the dibutyl di para-toluolsulfonamide tin of the formula:

04m mozs ctm o-m Sn 04410 \HNO2S-COH4'CH3 which theoretically requires 20.7 per cent of tin.

Example 2 64 g. of N-butyl benzenesulfonamide, 12.6 g. of caustic soda pellets dissolved in 12 cc. water and 1200 cc. xylol were refluxed and treated in a similar manner as in the preceding example.

04H. NOaSCs s /Sn\ I 04H. N O:SCGH5 Example 3 33 g. of n-hexane sulfonamide were added to a solution of 4.6 g. of sodium metal in 160 cc. of absolute methanol under cooling at 10 C. To this solution 30.4 g. of dibutyl tin dichloride dissolved in 40 cc. of methanol was added at -10 C.

and the mixture was stirred until it became neutral; The salt Was filtered off and the methanol removed under reduced pressure. The product obtained was a viscous liquid and contained predominantly the dibutyl di n-hexane sulfonamide tin of the formula Example 4 In an analogous manner, as described in the first example, dibutyl tin di-benzene sulfonamide 'was prepared having the formula The crude product obtained after removing the solvent was purified by extraction with ether, then recrystallized from hot toluene. The product obtained was analyzed and contained:

HNOzS-CaHg theory, found, percent percent Tln-- 21 55 21. 7 Nitro en 5. 13 4. 98

I 'he melting point was 135-137 0.

Example 5 The sodium derivative of N-ethyl p-toluolsul- 'fonamide, prepared by an azeotropic distillation of 39.8 g. N-ethyl p-toluolsulfonamide with 8 g.

of sodium hydroxide in 200 cc. xylol was reacted under cooling with 65 g. of tributyl tin monochloride until the reaction became neutral. After filtering on the salt formed in the reaction, the solvent was removed under reduced 'pressure and the liquid tin derivative frac- :tionated. The fraction boiling at 200 C. at

1.5 mm. was a clear colorless liquid which on analysis gave the following results:

found, theory, percent percent Sn-.- 24.1 8 24.3 N 2.80 2.87

It corresponded to the formula 04H: CzHl C4Hr-SIl-NO1SC9H4CH3 .CHB

In the examples, we have shown the preparation of alkyl tin sulfonamides because the alkyl tin halides used as starting material are more readily available in commerce than the corresponding aryl tin halides. We have found, however, that aryl tin sulfonamides, such as di or tri phenyl, benzyl, tolyl, xylyl, and similar sulfonamides can be prepared in the same way as the alkyl tin sulfonamides.

Though we have herein set forth specific embodiments of our invention, it is not our intention to be limited thereto. To those skilled in the art there will be apparent many obvious variations and modifications such as the variations of quantities used and a substitution of equivalent materials that do not depart from the scope of our invention as set forth in the appended claims.

What we claim is:

1. An organo-tin sulfonamide useful as a stabilizer for vinyl halide resins,'of the formula RmSn(R'NOzSR")n, wherein the tin atom is directly connected to the nitrogen atom of the sulfonamido group and R represents an alkyl radical having 1 to 12 carbon atoms, R is a member selected from the group consisting of hydrogen, alkyl, and aryl, R" is a member of the group consisting of alkyl, aryl, and aralkyl, and wherein m+n is 4, m being an integer from 2 to 3.

2. A dialkyl tin sulfonamide useful as a stabilizer for vinyl halide resins, of the formula R2Sn(RNO2SR")z, wherein R represents an alkyl radical having 1 to 12 carbon atoms, R is a member selected from the group consisting of hydrogen, alkyl and aryl, and R is a member of the group consisting of alkyl, aryl, and aralkyl.

GERRY P. MACK. EMERY PARKER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,135,553 Andersen Nov. 8, 1938 2,452,595 Mowery, Jr. Nov. 2, 1948 OTHER REFERENCES 

1. AN ORGANO-TIN SULFONAMIDE USEFUL AS A STABILIZER FOR VINYL HALIDE RESINS, OF THE FORMULA RMSN(R1NO2SR")N, WHEREIN THE TIN ATOM IS DIRECTLY CONNECTED TO THE NITROGEN ATOM OF THE SULFONAMIDO GROUP AND R REPRESENTS AN ALKYL RADICAL HAVING 1 TO 12 CARBON ATOMS, R'' IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL, AND ARYL, R" IS A MEMBER OF THE GROUP CONSISTING OF ALKYL, ARYL, AND ARALKYL, AND WHEREIN M+N IS 4, M BEING AN INTEGER FROM 2 TO
 3. 